CN103299242B

CN103299242B - Photocurable resin composition, its dry film and solidfied material and use their printed circuit board (PCB)

Info

Publication number: CN103299242B
Application number: CN201180063164.3A
Authority: CN
Inventors: 峰岸昌司; 有马圣夫
Original assignee: Taiyo Ink Mfg Co Ltd
Current assignee: Taiyo Holdings Co Ltd
Priority date: 2010-12-28
Filing date: 2011-06-17
Publication date: 2016-08-10
Anticipated expiration: 2031-06-17
Also published as: JP5876925B2; JPWO2012090532A1; TWI514074B; CN103299242A; WO2012090532A1; JP2015064612A; TW201227172A; JP5771221B2; KR20160003294A; KR20130099219A

Abstract

Even if for the generation of crackle of solder mask produced when a large amount of compounding fillers are also good as the process of solder resist and can suppress cold cycling, stripping, the Photocurable resin composition that Tong Guo the aqueous slkali of the present invention develops is to comprise containing carboxyl oligomer, the compositions of high polymer binder, Photoepolymerizationinitiater initiater, photopolymerization monomer and filler that the above-mentioned oligomer containing carboxyl of molecular weight ratio is big, and the content of above-mentioned filler is 30～60 mass % of the nonvolatile component total amount of compositions.Desirably, above-mentioned high polymer binder is thermoplastic resin, preferably the thermoplastic resin solution that solid constituent is 10～50wt% when being dissolved in solvent.Above-mentioned Photocurable resin composition or its dry film can be advantageously applied to the cured films such as the soldering-resistance layer of formation printed circuit board (PCB).

Description

Photocurable resin composition, its dry film and solidfied material and use their printed circuit board (PCB)

Technical field

The present invention relates to the uses such as solder resist as tellite Photocurable resin composition, Its dry film and solidfied material and employ their printed circuit board (PCB).

Background technology

In recent years, corresponding to the densification of the printed circuit board (PCB) of compactization along with electronic equipment, Solder resist is also required that operability, high performance.Additionally, recently, along with electronic equipment miniaturization, Lightweight, high performance, the miniaturization of semiconductor package body, spininess be practical, batch productionization Development.Corresponding such densification, replaces being referred to as QFP (encapsulation of Quad Flat formula), SOP (little Outline packages) etc. IC encapsulation, occur in that be referred to as BGA (BGA Package), CSP (chip size seal Dress) etc. IC encapsulation.As the welding resistance used in such base plate for packaging, vehicle-mounted printed circuit board (PCB) Agent, at present, discloses various Photocurable resin composition (referring for example to patent documentation 1).

High insulating reliability is required for insulant such as solder resists, therefore specially requires and also should be referred to as moisture-proof The hot Cooker of resistance to PCT(Pressure Test, pressure cooker testing) property.On the other hand, from productivity ratio From the viewpoint of, also require that ultraviolet etc. reactive, high that solder resist uses when having patterning Exposure sensitivity.

But, more than existing liquid developable solder flux there is also for aforementioned claim characteristic and should improve Ground.Further, there are the following problems for existing liquid developable solder flux: when packaging body is installed, by In the moisture absorption of solder resist, the moisture of package interior moisture absorption seethes with excitement in Reflow Soldering, package interior Welding resistance epithelium and periphery crack.Further, in the packaging body being applied with solder mask, close During envelope IC chip, IC substrate and solder mask are applied heat, due to the expansion system of substrate and solder mask when driving Number is different and easily cracks, peel off.

For such technical problem, have and be compounded in a large number in the photosensitive polymer combination of solder resist The trial (with reference to patent documentation 2) of filler.The present inventor etc. also confirm in photosensitive polymer combination big During amount compounding filler, the apparent patience of the film obtained, water absorption rate reduce, join in significant amount In the case of Hun, except, the adaptation fall of film many relative to the situation of adherend filler self-contact Outside low problem, the mobility of compositions is significantly deteriorated.Particularly it is compounded together with photopolymerization monomer Time, become dilatant fluid, become the state that even can not be stirred, apply.It addition, such as welding resistance In the such negative light-sensitive resin combination of agent, exist owing to the impact of filler is for the peristome of path Sufficient resolution can not be obtained, problem that halation peristome due to light becomes the state closed.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Laid-Open Patent Publication 61-243869 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2000-181058 publication

Summary of the invention

The problem that invention is to be solved

Therefore, it is an object of the invention to provide a kind of Photocurable resin composition, even if joining in large quantities Mixed filler is also unlikely to cause the reduction of the adaptation of compositions, mobility, and the coating to base material is easy, By reducing the linear expansion coefficient of solder resist, it is possible to the crackle of the solder resist produced during suppression cold cycling Produce, peel off.

It addition, the invention reside in offer Photocurable resin composition, it can improve existing printing electricity The solder resist of road plate, the required resolution such as interlayer dielectic of multilayer circuit board, chemically-resistant are gold-plated Property, result from the characteristic such as resistance to PCT of adaptation, and particularly can obtain required by IC encapsulation The cured film of excellent, it is possible to the reply densification of printed circuit board (PCB), face installationization, it is possible to logical Cross alkali development and form the opening of path.

It is a further object of the invention to provide by the such Photocurable resin composition of use The dry film of the as described above all excellents obtained and solidfied material and formed by this dry film, solidfied material The printed circuit board (PCB) of the cured films such as soldering-resistance layer.

For solving the scheme of problem

In order to reach object defined above, according to the present invention, it is provided that a kind of photocuring developed by aqueous slkali Property resin combination, it is characterised in that said composition comprises containing carboxyl oligomer, molecular weight ratio is above-mentioned contains High polymer binder, Photoepolymerizationinitiater initiater, photopolymerization monomer and the filler that carboxyl oligomer is big, on State 30～60 mass % of the nonvolatile component total amount that content is compositions of filler.

According to preferred mode, above-mentioned high polymer binder is thermoplastic resin, is preferably dissolved in solvent Solid constituent under state is the thermoplastic resin solution of 10～50wt%.According to other preferred modes, Above-mentioned filler comprises Ba or comprises Mg and/or Al.

It addition, according to the present invention, also provide for being coated with aforementioned Photocurable resin composition on a carrier film And be dried and the dry film of the photo-curable that obtains, aforementioned Photocurable resin composition or this dry film passed through Solidfied material that the irradiation of active energy beam carries out photocuring and obtains, particularly make its photocuring on copper And the solidfied material obtained, be light-cured into pattern-like and obtain solidfied material.In one mode, dry film is by multilayer optical The drying layer of hardening resin composition is formed, and at least one of which is by the aforementioned light-cured resin group of the present invention Compound is formed.

Further, according to the present invention, also provide for a kind of printed circuit board (PCB), it is characterised in that it has solid Changing epithelium, described cured film is aforementioned Photocurable resin composition or dry film to be penetrated by active-energy The irradiation of line is light-cured into pattern-like, preferably further carries out heat cure and obtains.

The effect of invention

The Photocurable resin composition of the present invention, due to the nonvolatile component that content is compositions of filler 30～60 mass % of total amount, therefore, it is possible to the linear expansion coefficient of target solidfied material is regulated 15～35 × 10^-6/ K(is hreinafter referred to as ppm) in the range of, by making it consistent with the linear expansion coefficient of substrate Or it is close, it is possible to reduce the generation of the crackle of solder resist.Further, more oligomeric than containing carboxyl by adding The binding agent of the taller molecular weight of thing, solves and produces such as when being compounded substantial amounts of filler: compositions close The problems such as the process crackle when reduction of conjunction property, mobility reduction, the reduction of film formative, film forming, and its Solidfied material can obtain the resolution of excellence, rise when being applied to such as printed circuit board (PCB), semiconductor packages Because of in the resistance to PCT etc. of adaptation, it is possible to obtain high reliability.

Detailed description of the invention

The Photocurable resin composition that Tong Guo the aqueous slkali of the present invention develops is (solid hereinafter also referred to as light The property changed resin combination) it is characterised by, it is above-mentioned containing carboxylic for comprising containing carboxyl oligomer, molecular weight ratio The combination of high polymer binder, Photoepolymerizationinitiater initiater, photopolymerization monomer and filler that base oligomer is big Thing, the content of above-mentioned filler is 30～60 mass % of the nonvolatile component total amount of compositions.

Hereinafter, each constituent of the Photocurable resin composition of the present invention is described in detail.

The Photocurable resin composition of the present invention can give alkali development by using containing carboxyl oligomer Property.It should be noted that in this specification, term " oligomer " should be appreciated that and becomes and macromolecule Binding agent readily distinguishes molecular weight and uses.As containing carboxyl oligomer, it is possible to use molecule has There are carboxyl existing known various containing carboxy resin or prepolymer.Especially, from photo-curable, resistance to aobvious From the point of view of the aspect of shadow, more preferably molecule has ethylenical unsaturated double bonds containing carboxyl photoresist or Person's photonasty prepolymer Han carboxyl.Further, its unsaturated double-bond is preferably derived from acrylic or methacrylic Acid or their derivant.It should be noted that only use do not have ethylenical unsaturated double bonds containing carboxylic When base resin or prepolymer, in order to make compositions be photo-curable, need to be applied in combination molecule described later In there is the compound of multiple ethylenically unsaturated group, i.e. photopolymerization monomer.

As the concrete example containing carboxyl oligomer, can suitably use the oligomer being exemplified below.

(1) by the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methyl styrene, (first Base) lower alkyl acrylate, isobutene. etc. obtain containing the copolymerization of unsaturated group compound containing carboxylic Base oligomer.

(2) by aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type two isocyanide The diisocyanate such as acid esters, aromatic diisocyanate contains with dihydromethyl propionic acid, dimethylolpropionic acid etc. Carboxylic diol compound and polycarbonate-based polyhydric alcohol, polyethers system polyhydric alcohol, polyester-based polyols, poly- Olefin-based polyhydric alcohol, acrylic acid series multiple alcohol, bisphenol-A system alkylene oxide addition product dihydroxylic alcohols, there is phenol The sudden reaction of the diatomic alcohol compounds such as the compound of hydroxyl and alcohol hydroxyl group and obtain containing the poly-ammonia of carboxyl Ester resin.

(3) by diisocyanate and bisphenol A type epoxy resin, bisphenol-A epoxy resin, double Phenol F type epoxy resin, bisphenol-s epoxy resin, di-toluene phenol-type epoxy resin, biphenyl phenolic epoxy (methyl) acrylate of resin etc. 2 functional epoxy resins or the anhydride modified thing of its part, carboxylic Diol compound and the sudden reaction of diatomic alcohol compounds and obtain containing carboxyl photonasty polyurethane tree Fat.

(4) in the synthesis of above-mentioned (2) or the resin of (3), (methyl) acrylic acid hydroxy alkyl ester etc. is added at molecule In there is the compound an of hydroxyl and more than one (methyl) acryloyl group and the end (methyl) third that obtains Alkene is acylated containing carboxyl photonasty polyurethane resin.

(5) by adding isophorone diisocyanate in the synthesis of aforementioned (2) or the resin of (3) Ester has 1 NCO and 1 in the reaction with same mole thing equimolecular of pentaerythritol triacrylate The compound of individual above (methyl) acryloyl group and the end (methyl) that obtains acrylated containing carboxylic Base photonasty polyurethane resin.

(6) by aftermentioned such 2 officials can or 2 officials can above multifunctional (solid-state) epoxy resin with (methyl) acrylic acid reacts, and is present in hydroxyl and phthalic anhydride, the tetrahydrophthalic acid of side chain 2 yuan of anhydride additions such as acid anhydride, hexahydrophthalic anhydride and obtain containing carboxyl photonasty oligomer.

(7) use epoxychloropropane that the hydroxyl of aftermentioned such 2 officials' energy (solid-state) epoxy resin is entered one The polyfunctional epoxy resin walking epoxidation and obtain reacts with (methyl) acrylic acid, the hydroxyl of generation and 2 Unit anhydride addition and obtain containing carboxyl photonasty oligomer.

(8) by make aftermentioned such 2 officials can oxetane resins and adipic acid, phthalic acid, The reaction of the dicarboxylic acids such as hexahydrophthalic acid, and make generated primary hydroxyl and dibasic acid anhydride carry out addition and Obtain containing carboxyl polyester oligomer.

(9) make containing unsaturated group monocarboxylic acid with, by 1 molecule has the compound of multiple phenolic hydroxyl group with The reaction of the alkylene oxide such as oxirane, expoxy propane and the product that obtains carries out reacting so as to get anti- Answer the polyprotic acid such as product and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride Anhydride reactant and obtain containing carboxyl photonasty oligomer.

(10) make containing unsaturated group monocarboxylic acid with, by 1 molecule has the compound of multiple phenolic hydroxyl group with The product that the cyclic carbonate compound such as ethylene carbonate, propylene carbonate reacts and obtains is carried out instead Should, the product obtained is reacted with multi-anhydride and obtain containing carboxyl photonasty oligomer.

(11) by making the resin of above-mentioned (1)～(10) have 1 epoxy with 1 molecule further Base and the compound addition of more than 1 (methyl) acryloyl group and obtain containing carboxyl photonasty oligomer.

It should be noted that in this specification, (methyl) acrylate refers to general name acrylate, first Base acrylate and the term of their mixture, other similar performances are too.

Aforementioned containing carboxyl oligomer owing to having multiple carboxyl on the side chain of trunk polymer, it is thus possible to Developed by dilute alkaline aqueous solution.

It addition, the aforementioned acid number containing carboxyl oligomer 40～200mgKOH/g scope be suitable, More preferably 45～120mgKOH/g scope.Acid number containing carboxyl oligomer is less than 40mgKOH/g Time, alkali development becomes difficulty, on the other hand, during more than 200mgKOH/g, because developer solution causes exposure The dissolving aggravation in portion, line is beyond thin necessarily, or according to circumstances, exposure portion is as broad as long with unexposed portion Ground is peeled off by developing solution dissolution, draws normal corrosion-resisting pattern and becomes difficulty, thus the most preferred.

Additionally, the aforementioned weight average molecular weight containing carboxyl oligomer is different according to resin matrix, generally exist 2000～150000, further preferably 5000～100000 scope.Need to use weight average molecular weight ratio Use high polymer binder low containing carboxyl oligomer, particularly preferred weight average molecular weight be 5000～ 35,000.When weight average molecular weight is less than 2000, the non-adhesion behavior of film is deteriorated, the film after exposure resistance to Moist variation, produces film and reduces during development, resolution becomes very poor.On the other hand, weight average molecular weight surpasses After 150000 time, developability is significantly deteriorated.It addition, bigger than high polymer binder described later time, it is impossible to change The fragility of kind target film.

Such 10～60 mass % that compounding amount is total composition containing carboxyl oligomer, be preferably 20～ The scope of 50 mass % is applicable.When compounding amount containing carboxyl oligomer is less than above-mentioned scope, epithelium is strong Degree reduces, therefore the most preferred.On the other hand, during more than above-mentioned scope, the viscosity of compositions uprises, coating Property etc. reduce, therefore the most preferred.

These oligomer Han carboxyl are not limited to the material of aforementioned list, it is possible to use a kind can also mix Multiple use.Especially aforementioned containing in carboxyl oligomer, the refractive index of the resin with aromatic rings is high, Excellent in resolution, thus be preferred, further, the resin with biphenyl novolac structure not only divides Resolution, resistance to PCT, resistance to anti-thread breakage also excellence, thus be preferred.It addition, as containing carboxyl photonasty Oligomer (9), (10) are such use phenolic compounds as initial feed containing carboxyl oligomer, similarly Resistance to PCT improve, therefore it is also preferred that.Normally, due to the increase of filler composition, filler and resin Interface easily absorbs water, in contrast, have the resin of biphenyl novolac structure, as (9), (10) that Even if the resistance to PCT of increase containing carboxyl oligomer filler composition of sample is the most excellent.This be considered as by In, because of the structure of xenol Novolac, hydrophobicity improves for the former；For the latter it is considered to be due to phase For forming the similar photonasty oligomer containing carboxyl (6) of structure, (7) are epoxy acrylate knot Structure also has hydroxyl, and the photonasty oligomer containing carboxyl (9), (10) do not have hydroxyl, hydrophobicity to significantly improve.

As aforementioned high polymer binder, the most reactive or non-reacted, as long as thermoplastic resin Then there is no particular limitation, it is possible to uses such as: polyphenylene sulfide, polyarylate, polysulfones, polyether sulfone, poly- The thermoplastic resin such as ether ether ketone, polyether-ketone；TPI, it is referred to as the fragrance of phenoxy resin Same clan's resin group；Ethyl cellulose, cellulose acetate, acetyl propyl cellulose, acetyl tributyl cellulose Deng cellulose derivative；By molten for the ethenyl derivatives such as various acrylate, styrene, vinylacetate Liquid polymerization, suspension polymerisation and the polymer etc. that obtains.Alternatively, it is also possible to use by using two or more The monomer with vinyl carry out being polymerized and obtain bipolymer, terpolymer, block copolymerization Thing etc..In these polymer, the material that particularly preferably obtained by cellulose derivative, block copolymer. The preferred molecular weight of high polymer binder, with Weight-average molecular gauge, is 30000～1500000, as long as sentence The situation being set to molecular weight substantially big than the oligomer containing carboxyl used just can use.Such as, it is dissolved in Situation high with viscosity compared with carboxyl oligomer during same solvent.Further, usual molecular weight is the biggest The lowest relative to the dissolubility of solvent, when the amount of solid constituent when being therefore dissolved in same solvent is low, special It not when 10～50wt%, to be judged to that the aforementioned oligomer containing carboxyl of molecular weight ratio is big.Solid constituent compares 10wt% Time few, produce the problem that solvent composition increase can not form compositions.On the other hand, solid constituent ratio When 50wt% is many, there is the high molecular situation that is not belonging to, the most appropriate.

The effect of these high polymer binders can list several.One, changes the mobility of compositions. When specifically describing in detail, when being compounded substantial amounts of filler in containing carboxyl oligomer and photopolymerization monomer, particularly Photopolymerization monomer and the poor compatibility of filler, the compositions obtained become dilatant fluid.Compositions becomes When becoming swollen plasticity, there are the following problems: is difficult to compositions be stirred, print or apply, is not certain Diluted state can not use, and particularly silk screen printing, roller coat such as applies at the print that carries out under higher viscosity Brush, one-step print cannot ensure the thickness of necessity.If now adding high polymer binder, compositions energy Enough to thixotropic fluid transformation.The most tentatively become the material that can print, apply.Second definite effect When making dry film state for compositions being applied, being dried, it is possible to control processes crackle.May be considered because of For having the effect that will anchor in a large number compounded with the filler of high polymer binder.High polymer binder adds 3rd effect is in physical property after hardening, it is possible to increase the toughness of film.It is believed that be because high score Sub-binding agent in light-cured resin substrate with IPN(island) state exist.According to above 3 reasons By, it is believed that after adding high polymer binder, even if being total at photopolymerization monomer and substantial amounts of filler In the compositions deposited, print and apply become possibility, linear expansion coefficient reduce, tough painting can be obtained Film.

It addition, these high polymer binders can also exist on end and/or side chain carboxyl, hydroxyl, The functional groups such as epoxy radicals.As the amount of preferred carboxyl, acid number is below 30mgKOH/g.

Relative to aforementioned containing carboxyl oligomer 100 mass parts, the preferably compounding amount of high polymer binder is 1 matter More than amount part.So, only need to add a small amount of high polymer binder just can fully realize the stream of compositions Dynamic property.Further for fully improving physical property, further amounts of high polymer binder can be added, its upper limit It is to be suitable about 30 mass parts relative to the mass parts containing carboxyl oligomer 100.High polymer binder When addition is too much, developability is significantly deteriorated, and remains being formed on the circuit of substrate of circuit, between circuit There is residue, now the coating of Photocurable resin composition is divided 2 times and carry out, be coated with during primary coating Cloth do not comprise high polymer binder compositions or coating comprise less than 5 mass parts macromolecule bond The compositions of agent, is coated with compounded with high polymer binder and the compositions of the present invention of mass filler afterwards, The problem that this addresses the problem poor visualization.Similarly, the layer knot of more than 2 layers is also made when forming dry film Structure, directly contact with base material the layer of side formed with the composition layer that there is not high polymer binder or There is ratio with high polymer binder to be formed less than the composition layer of 5 mass parts, more to contain high score The composition layer of the present invention of sub-binding agent forms other layer etc., it is possible to solve problem.

As the Photoepolymerizationinitiater initiater used in the Photocurable resin composition of the present invention, can suitably make With choosing, freely there is the oxime ester system Photoepolymerizationinitiater initiater of oxime ester base, the photopolymerization initiation of alpha-aminoacetophenone system In the group that agent, acylphosphine oxide system Photoepolymerizationinitiater initiater form more than a kind.

As the commercially available product of oxime ester system Photoepolymerizationinitiater initiater, can list what BASF JAPAN company manufactured CGI-325, IRGACURE (registered trade mark) OXE01, IRGACURE OXE02, ADEKA are public N-1919, NCI-831 etc. that department manufactures.Furthermore it is also possible to be preferably used in molecule, there are 2 oxime ester bases Photoepolymerizationinitiater initiater, specifically, the oxime with carbazole structure represented by following formula can be listed Ester compounds.

[chemical formula 1]

(in formula, X represent hydrogen atom, the alkyl of carbon number 1～17, the alkoxyl of carbon number 1～8, phenyl, Phenyl (by the alkyl of carbon number 1～17, the alkoxyl of carbon number 1～8, amino, has the alkane of carbon number 1～8 The alkylamino of base or dialkylamino replace), naphthyl is (by the alkyl of carbon number 1～17, the alcoxyl of carbon number 1～8 Base, amino, the alkylamino with the alkyl of carbon number 1～8 or dialkylamino replace), Y, Z each represent Hydrogen atom, the alkyl of carbon number 1～17, the alkoxyl of carbon number 1～8, halogen group, phenyl, phenyl (quilt The alkyl of carbon number 1～17, the alkoxyl of carbon number 1～8, amino, there is the alkane ammonia of the alkyl of carbon number 1～8 Base or dialkylamino replace), naphthyl (by the alkyl of carbon number 1～17, the alkoxyl of carbon number 1～8, amino, There is the alkylamino of the alkyl of carbon number 1～8 or dialkylamino replace), anthryl, pyridine radicals, benzofuran Base, benzothienyl, Ar represents singly-bound or the alkylidene of carbon number 1～10, ethenylidene, sub-benzene Base, biphenylene, pyridylidene, naphthylene, thienyl, anthrylene, sub-thienyl, furylidene, 2,5-pyrroles-diyl, 4,4 '--diyl, 4,2 '-styrene-diyl, n is the integer of 0 or 1.

Particularly, in aforementioned formula, it is preferred that X, Y are respectively methyl or ethyl, Z be methyl or Phenyl, n is 0, and Ar is singly-bound or phenylene, naphthylene, thienyl or sub-thienyl.

Relative to 100 mass parts oligomer Han carboxyl, the compounding amount of such oxime ester system Photoepolymerizationinitiater initiater It is preferably 0.01～5 mass parts.During less than 0.01 mass parts, the photo-curable on copper is insufficient, film Peeling-off, and the coating characteristic such as chemical proofing reduces.On the other hand, during more than 5 mass parts, The light having film coated surface absorbs and becomes acutely, the tendency that deep curable reduces.More preferably 0.5～3 mass Part.

As alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, 2-methyl isophthalic acid-[4-(first can be listed specifically Base sulfur generation) phenyl-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) -butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl ］-1-[4-(4-morpholinyl) Phenyl ］-1-butanone, N, N-dimethylamino benzoylformaldoxime etc..As commercially available product, BASF can be listed Irgacure907, Irgacure369, Irgacure379 etc. that JAPAN company manufactures.

As acylphosphine oxide system Photoepolymerizationinitiater initiater, 2,4,6-trimethylbenzene first can be listed specifically Acyl group diphenyl phosphine oxide, double (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, double (2,6-dimethoxy Benzoyl)-2,4,4-trimethyl-pentyl phosphine oxide etc..As commercially available product, BASF JAPAN can be listed The Lucirin TPO of company, the IRGACURE819 etc. of BASF JAPAN.

Relative to 100 mass parts oligomer Han carboxyl, these alpha-aminoacetophenone system Photoepolymerizationinitiater initiaters, The compounding amount of acylphosphine oxide system Photoepolymerizationinitiater initiater is preferably 0.01～15 mass parts.Less than 0.01 mass Part time, the photo-curable on copper equally is insufficient, and film is peeled off, and the film such as chemical proofing Characteristic reduces.On the other hand, time more than 15 mass parts, it is impossible to obtain the reducing effect of degassing, further The light having film coated surface absorbs and becomes acutely, has the tendency that deep curable reduces.More preferably 0.5～10 Mass parts.

Here, as the Photoepolymerizationinitiater initiater used, the addition of above-mentioned oxime ester series initiators is also few, Can suppression degassing, therefore, to resistance to PCT, resistance to anti-thread breakage effectively, therefore preferably.It addition, in oxime ester system When being applied in combination acylphosphine oxide system Photoepolymerizationinitiater initiater on the basis of initiator, resolution can be obtained good Shape, the most particularly preferably.

It addition, the photopolymerization as the Photocurable resin composition that can be preferred for the present invention causes Agent, light-initiated auxiliary agent and sensitizer, can list benzoin compound, acetophenone compound, anthraquinone Compound, thioxanthone compounds, ketal compound, benzophenone cpd, tertiary amine compound and Ton ketonic compound etc..

As benzoin compound, specifically, include, for example out benzoin, benzoin methylether, benzene Benzoin ethyl ether, benzoin iso-propylether etc..

As acetophenone compound, specifically, include, for example out 1-Phenylethanone., 2,2-dimethoxy-2- Phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone etc..

As anthraquinone compounds, specifically, include, for example out 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone etc..

As thioxanthone compounds, specifically, include, for example out 2,4-dimethyl thioxanthone, 2,4- Diethyl thioxanthone, CTX, 2,4-diisopropylthioxanthone etc..

As ketal compound, specifically, include, for example out 1-Phenylethanone. dimethyl ketal, benzil Dimethyl ketal etc..

As benzophenone cpd, specifically, such as benzophenone, 4-benzoyl can be listed Diphenylsulfide, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 4-benzoyl-4 '-ethyl diphenyl Thioether, 4-benzoyl-4 '-propyl group diphenylsulfide etc..

As tertiary amine compound, specifically, such as there is ethanolamine compound, there is dialkyl amido benzene The compound of structure, such as, commercially available product can list 4,4 '-dimethylamino benzopheone (Japan Cao Da Company manufacture NISSOCURE MABP), 4,4 '-lignocaine benzophenone (Hodogaya Chemical Co., LTD. manufacture EAB) etc. dialkyl amido benzophenone, 7-(lignocaine)-4-first Base-2H-1-chromen-2-ones (7-(lignocaine)-4-methylcoumarin) etc. are containing dialkyl amido Coumarin compound, the ethyl 4-dimethy laminobenzoate (KAYACURE that chemical medicine company of Japan manufactures (registered trade mark) EPA), 2-dimethylamino ethyl benzoate (International Bio-Synthetics Company manufacture Quantacure DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (the Quantacure BEA that International Bio-Synthetics company manufactures), dimethylamino is rested in peace Fragrant acid isopentyl ethyl ester (the KAYACURE DMBI that chemical medicine company of Japan manufactures), 4-dimethylamino peace Breath fragrant acid 2-Octyl Nitrite (Esolol507 that Van Dyk company manufactures), 4,4 '-lignocaine hexichol first Ketone (EAB that Hodogaya Chemical Co., LTD. manufacture) etc..

In the middle of these, preferably thioxanthone compounds and tertiary amine compound.Particularly, from deep curable Aspect is set out and is preferably comprised thioxanthone compounds.Particularly preferably comprise 2,4-dimethyl thioxanthone, 2,4-diethyl The thioxanthone compounds such as base thiaxanthone, CTX, 2,4-diisopropylthioxanthone.

As the compounding amount of such thioxanthone compounds, relative to 100 mass parts oligomer Han carboxyl, It is preferably below 20 mass parts.When the compounding amount of thioxanthone compounds is more than 20 mass parts, thick film curable Reduce, and the cost of goods can be caused to increase.Below more preferably 10 mass parts.

It addition, as tertiary amine compound, preferably there is the compound of dialkylamino benzene structure, the most especially Preferably dialkylamino benzophenone cpd, maximum absorption wave a length of 350～450nm containing dialkylamino Coumarin compound and coumarin ketone.

As dialkylamino benzophenone cpd, 4,4 '-lignocaine benzophenone is because toxicity is the lowest Preferably.Coumarin compound containing dialkyl amido due to maximum absorption wave a length of 350～410nm, Ultraviolet range, therefore can provide coloring less, water white photosensitive composite be mathematical, Can also provide and use coloring pigment and reflect the coloring soldering-resistance layer of color of coloring pigment itself.From right The sensitization effect of the laser display excellence of wavelength 400～410nm is set out, particularly preferred 7-(lignocaine) -4-methyl-2H-1-chromen-2-one.

As the compounding amount of this tertiary amine compound, relative to 100 mass parts oligomer Han carboxyl, preferably It is 0.1～20 mass parts.When the compounding amount of tertiary amine compound is less than 0.1 mass parts, has and cannot obtain fully The tendency of sensitization effect.During more than 20 mass parts, tertiary amine compound is had to cause at dry welding resistance film The light on surface absorbs aggravation, there is the tendency that deep curable reduces.More preferably 0.1～10 mass parts.

These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer can be used alone or as 2 kinds Above mixture uses.

Aforementioned relative to 100 mass parts containing carboxyl oligomer, this Photoepolymerizationinitiater initiater, light-initiated auxiliary agent It is preferably below 35 mass parts with the total amount of sensitizer.During more than 35 mass parts, exist and absorbed by these light Cause the tendency that deep curable reduces.

It addition, these Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer are owing to absorbing specific ripple Long, thus reduce sensitivity sometimes according to situation, play the effect of UV absorbent.But, they Not it is only used for improving the purpose of the sensitivity of compositions.Specific wavelength can also be absorbed as required Light, improves the photoreactivity on surface, makes the wire shaped of resist layer (resist) and opening become vertically, bore Shape, inverted cone shape, improve live width, the machining accuracy in opening footpath simultaneously.

Filler can be compounded in the Photocurable resin composition of the present invention, for the compounding of filler measure into Row in detail research it was found that 30～60 mass % of nonvolatile component total amount by adding compositions Filler, resistance to PCT, electrical characteristics (HAST patience) improve.Further, it is possible to know the folding of filler When rate of penetrating is in the range of 1.50～1.65, height accelerated aging (is tried by the most resistance to PCT, HAST patience The patience tested) excellent, and good resolution can be obtained.As obtaining high-resolution reason, It is considered refractive index and the filler of the resin with aromatic rings for improving resistance to PCT, HAST patience Refractive index close.

As the filler can being applied in the present invention, such as can use barium sulfate, Talcum, clay, Magnesium carbonate, calcium carbonate, aluminium oxide, aluminium hydroxide, boehmite, mica powder, brucite etc. are known usual Inorganic filler.According to preferred mode, above-mentioned filler comprises Ba or comprises Mg and/or Al.Especially It is, as the filler containing Ba, and preferably barium sulfate (refractive index: 1.65), as the filler containing Mg, Preferably talc (refractive index: 1.54-59), magnesium carbonate (refractive index: 1.57-1.60), as the filler containing Al, Preferably Kaolin, clay (refractive index: 1.55-1.57), aluminium oxide (refractive index: 1.65), aluminium hydroxide (folding Penetrate rate: 1.65), boehmite (refractive index: 1.62-1.65), mica powder (refractive index: 1.59), as containing The filler of Mg and Al, preferably brucite (refractive index: 1.50).

The total amount of filler is in 30～60 mass % of the nonvolatile component total amount of Photocurable resin composition Scope be suitable.When the content of filler is less than 30 mass %, the solidification of Photocurable resin composition There is not the reduction of linear expansion coefficient, resistance to anti-thread breakage variation in thing, the most preferred.On the other hand, fill out When the content of material is more than 60 mass %, the viscosity of compositions uprises, and coating, formability reduce, further Owing to water absorption also increases, resistance to PCT, HAST patience is deteriorated, the most preferred.It addition, these Filler can be used alone or be applied in combination two or more.

In the Photocurable resin composition of the present invention, preferably add sulfhydryl compound.Can confirm that and pass through Add sulfhydryl compound and improve resistance to PCT and HAST patience.May be considered owing to adding sulfhydrylation Compound, crosslink density improves, or adaptation improves.

Aforementioned relative to 100 mass parts containing carboxyl oligomer, the compounding amount of sulfhydryl compound is 0.01 mass parts Above and 10.0 mass parts the following is suitable, more preferably more than 0.05 mass parts and 5 mass parts with Under.During less than 0.01 mass parts, it is impossible to confirm carrying of the adaptation as sulfhydryl compound additive effect High；On the other hand, during more than 10.0 mass parts, exist and cause the development of Photocurable resin composition not The worry of management amplitude reduction good, dry etc., thus the most preferred.These sulfhydryl compounds can individually make With or be applied in combination two or more.

Heat curable component can be added in the Photocurable resin composition of the present invention.Can confirm that by adding Be heating and curing composition, and thermostability improves.As the heat curable component for the present invention, it is possible to use trimerization The amino resins such as melamine resin, benzoguanamine resin, melamine derivative, benzoguanamine derivant, Blocked isocyanate compounds, cyclic carbonate compound, multi-functional epoxy compound, multifunctional oxa-ring The known thermosetting such as butane compound, episulfide resin, bimaleimide resin, carbodiimides resin The property changed resin.Molecule particularly preferably has multiple cyclic ether group and/or cyclic thioether base (hereinafter referred to as For ring-type (sulfur) ether) heat curable component.

Such molecule has the heat curable component of multiple ring-type (sulfur) ether be molecule has multiple 3, Arbitrary group in ring-type (sulfur) ether of 4 or 5 rings or the compound of two kinds of groups, can list such as: Molecule has the compound of multiple epoxy radicals, i.e. multi-functional epoxy compound；Molecule has multiple oxygen The compound of azetidinyl, the most multifunctional oxetane compound；Molecule has multiple thioether group Compound, i.e. episulfide resin etc..

As described multi-functional epoxy compound, the ADK that such as ADEKA company manufactures can be listed CIZER O-130P、ADK CIZER O-180A、ADK CIZER D-32、ADK CIZER D-55 Deng epoxidized vegetable oil；Mitsubishi Chemical Ind manufacture jER(registered trade mark) 828, jER834, jER1001, EHPE3150, DIC that jER1004, DAICEL CHEMICAL INDUSTRIES, LTD. manufacture Company manufacture Epiclon(registered trade mark) 840, Epiclon850, Epiclon1050, Epiclon2055, Chemical company of Nippon Steel manufacture Epotote(registered trade mark) YD-011, YD-013, YD-127, D.E.R.317 that YD-128, Dow Chemical company manufactures, D.E.R.331, D.E.R.661, The Araldite6071 of D.E.R.664, BASF JAPAN company, Araldite6084, AralditeGY250, AralditeGY260, Sumitomo Chemical Co. Ltd. manufacture Sumiepoxy ESA-011, ESA-014, ELA-115, ELA-128, industrial group of Asahi Chemical Industry manufacture A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) bisphenol A type epoxy resin；Chemical company of Nippon Steel manufactures YDC-1312(trade name) etc. hydroquinone type epoxy resin；Chemical company of Nippon Steel manufactures YSLV-80XY(trade name) etc. bisphenol-type epoxy resin, chemical company of Nippon Steel manufacture YSLV-120TE(trade name) etc. thioether-type epoxy resin；Mitsubishi Chemical Ind manufacture jERYL903, Epiclon152, Epiclon165 that DIC company manufactures, the Epotote that chemical company of Nippon Steel manufactures YDB-400, YDB-500, D.E.R.542, the BASF JAPAN that Dow Chemical company manufactures is public Department manufacture Araldite8011, Sumitomo Chemical Co. Ltd. manufacture Sumiepoxy ESB-400, ESB-700, A.E.R.711, A.E.R.714 etc. (the being trade name) bromine that industrial group of Asahi Chemical Industry manufactures Change epoxy resin；JER152, jER154 that Mitsubishi Chemical Ind manufactures, Dow Chemical company manufactures D.E.N.431, D.E.N.438, DIC company manufacture Epiclon N-730, Epiclon N-770, Epiclon N-865, Epotote YDCN-701, YDCN-704 that chemical company of Nippon Steel manufactures, BASF JAPAN company manufacture Araldite ECN1235, Araldite ECN1273, Araldite ECN1299, Araldite XPY307, Japan chemical medicine company manufacture EPPN(registered trade mark)-201, EOCN(note Volume trade mark)-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Chemical Co. Ltd.'s system Sumiepoxy ESCN-195X, the ESCN-220 made, the A.E.R. that industrial group of Asahi Chemical Industry manufactures ECN-235, ECN-299 etc. (being trade name) phenolic resin varnish type epoxy resin；Chemical medicine company of Japan The biphenyl phenolic resin varnish type epoxy resins such as NC-3000, the NC-3100 manufactured；DIC company manufactures Epiclon830, jER807, the Epotote of chemical company of Nippon Steel manufacture that Mitsubishi Chemical Ind manufactures YDF-170, YDF-175, YDF-2004, the Araldite XPY306 that BASF JAPAN company manufactures Deng (being trade name) bisphenol f type epoxy resin；Chemical company of Nippon Steel manufacture EpototeST-2004, ST-2007, ST-3000(trade name) etc. bisphenol-A epoxy resin；Mitsubishi Chemical Ind manufactures JER604, EpototeYH-434, BASF JAPAN company that manufactures of chemical company of Nippon Steel manufactures The Sumiepoxy ELM-120 etc. that AralditeMY720, Sumitomo Chemical Co. Ltd. manufacture (is commodity Name) glycidyl amine type epoxy resin；The AralditeCY-350(business that BASF JAPAN company manufactures The name of an article) etc. hydantoin type epoxy resin；DAICEL CHEMICAL INDUSTRIES, LTD. system The Celoxide(registered trade mark made) 2021, BASF JAPAN company manufacture AralditeCY175, CY179 etc. (being trade name) alicyclic epoxy resin；YL-933, Dow that Mitsubishi Chemical Ind manufactures T.E.N., EPPN-501, EPPN-502 etc. (being trade name) three hydroxyphenyl of Chemical company Methane type epoxy resin；YL-6056, YX-4000, YL-6121(that Mitsubishi Chemical Ind manufactures are Trade name) etc. di-toluene phenolic or united phenol-type epoxy resin or their mixture；Japan's chemical medicine EPX-30, DIC company that EBPS-200, ADEKA company that company manufactures manufactures manufactures EXA-1514(trade name) etc. bisphenol-s epoxy resin；The jER157S(business that Mitsubishi Chemical Ind manufactures The name of an article) etc. bisphenol A novolac type epoxy resin；JERYL-931, BASF that Mitsubishi Chemical Ind manufactures (being trade name) the four hydroxy phenyl ethane type epoxy resin such as the Araldite163 that JAPAN company manufactures； Araldite PT810 (trade name), Nissan Chemical Industries company that BASF JAPAN company manufactures manufacture TEPIC(registered trade mark) etc. hetero ring type epoxy resin；The Blemmer(note that Nof Corp. manufactures Volume trade mark) the o-phthalic acid diglycidyl ester resin such as DGT；Chemical company of Nippon Steel manufactures The four glycidyl group dimethylbenzene ethane such as ZX-1063 (tetraglycidyl xylenoyl ethane) are set Fat；Chemical company of Nippon Steel manufacture ESN-190, ESN-360, DIC company manufacture HP-4032, The epoxy resin containing naphthyl such as EXA-4750, EXA-4700；DIC company manufacture HP-7200, HP-7200H etc. have the epoxy resin of bicyclopentadiene skeleton；Nof Corp. manufacture CP-50S, The glycidyl methacrylate such as CP-50M copolymerization system epoxy resin；And N-cyclohexylmaleimide Copolymerization epoxy resin with glycidyl methacrylate；Epoxide modified polybutadiene rubber derivant (PB-3600 etc. that such as DAICEL CHEMICAL INDUSTRIES, LTD. manufacture), CTBN Modified epoxy (YR-102, YR-450 etc. that such as chemical company of Nippon Steel manufactures) etc., but also It is not limited to these materials.These epoxy resin can be used alone or in combination of two or more kinds.Wherein, Particularly preferably phenolic resin varnish type epoxy resin, di-first phenol-type epoxy resin, united phenol-type epoxy resin, Xenol phenolic resin varnish type epoxy resin or their mixture.

As multifunctional oxetane compound, can list such as: double ［ (3-methyl-3-oxa-rings Butane group methoxyl group) methyl ether, double ［ (3-ethyl-3-oxetanylmethoxy) methyl ］ ether, Double ［ (3-methyl-3-oxetanylmethoxy) methyl ］ benzene of 1,4-, the double ［ (3-ethyl-3-oxa-of 1,4- Tetramethylene. ylmethoxy) methyl benzene, acrylic acid (3-methyl-3-oxetanyl) methyl ester, propylene Acid (3-ethyl-3-oxetanyl) methyl ester, methacrylic acid (3-methyl-3-oxetanyl) Methyl ester, methacrylic acid (3-ethyl-3-oxetanyl) methyl ester, their oligomer or copolymer Etc. multifunctional oxetanes class；And oxetanes alcohol and novolac resin, poly-(para hydroxybenzene Ethylene), cardo type bisphenols, calixarene kind, resorcinol calixarenes (calixresorcinarene) class, Or silsesquioxane (silsesquioxane) etc. has the etherate etc. of the resin of hydroxyl.Additionally, also The copolymer etc. of unsaturated monomer and (methyl) alkyl acrylate with oxa-ring fourth ring can be listed.

As molecule has the compound of multiple cyclic thioether base, include, for example out Mitsubishi Chemical Ind The bisphenol A-type episulfide resin YL7000 etc. manufactured.Same synthetic method is used alternatively, it is also possible to use The oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin is replaced to the episulfide resin etc. of sulphur atom.

Relative to carboxyl 1 equivalent containing carboxyl oligomer, such molecule has multiple ring-type (sulfur) The compounding amount of the heat curable component of ether is preferably 0.6～2.5 equivalents.When compounding amount is less than 0.6, soldering-resistance layer Middle residual carboxyl, thermostability, alkali resistance, electrical insulating property etc. reduce.On the other hand, during more than 2.5 equivalent, Owing to ring-type (sulfur) ether of low-molecular-weight remains in dry coating, it is coated with film strength etc. and reduces.More excellent Elect 0.8～2.0 equivalents as.

When using the heat curable component in molecule with multiple ring-type (sulfur) ether, preferably comprise heat cure and urge Agent.As such thermal curing catalyst, can list such as, imidazoles, 2-methylimidazole, 2-second Base imidazoles, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenyl miaow Azoles, 1-(2-cyanoethyl) imdazole derivatives such as-2-ethyl-4-methylimidazole；Dicyandiamide, benzyl dimethyl Amine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl group-N, N-dimethyl benzyl amine, 4-methyl-N, the hydrazides such as amines, adipic dihydrazide, sebacic dihydrazide such as N-dimethyl benzyl amine Compound；The phosphorus compounds etc. such as triphenylphosphine.It addition, as commercially available product, such as four countries can be listed 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ(of becoming industrial group to manufacture are miaow The trade name of azole compounds), the U-CAT(registered trade mark that SAN-APRO company manufactures) 3503N, U-CAT3502T(is the trade name of the blocked isocyanate compounds of dimethyl amine), DBU, DBN, U-CATSA102, U-CAT5002(are two ring type amidine compound and salt thereof) etc..Especially and not only It is limited to these compounds, as long as the heat of the thermal curing catalyst of epoxy resin, oxetane compound Curing catalysts or promote the material of epoxy radicals and/or oxetanyl and carboxyl reaction, Can be used alone or mix two or more and use.Further, it is also possible to use guanamines, methyl guanamines, benzene And guanamines, tripolycyanamide, 2,4-diaminourea-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4- Diaminourea-s-triazine, 2-vinyl-4,6-diaminourea-s-triazine isocyanuric acid adduct, 2,4-diaminourea-6- The Striazine derivatives such as methacryloxyethyl-s-triazine isocyanuric acid adduct, preferably by these The compound also worked as adaptation imparting agent is applied in combination with thermal curing catalyst.

As long as the ratio of the compounding amount amount commonly of these thermal curing catalysts is sufficient for, such as relative to 100 mass parts contain the heat curable component in carboxyl oligomer or molecule with multiple ring-type (sulfur) ether, It is preferably 0.1～20 mass parts, more preferably 0.5～15.0 mass parts.

Further, it is possible to be compounded coloring agent in the Photocurable resin composition of the present invention.As coloring Agent, it is possible to use the known coloring agent such as red, blue, green, yellow, can be pigment, dyestuff, pigment Any.Wherein, from reduce carrying capacity of environment and to human influence from the viewpoint of, preferably do not contain Halogen.

Red stain:

As red stain, have monoazo system, bisazo system, azo lake system, benzimidazolone system, System, diketopyrrolopyrrolecocrystals system, condensation azo system, anthraquinone system, quinacridone etc., specifically come Say, can list with following Colour Index (C.I.；The Society of Dyers and Colourists Distribution) material of sequence number.

Monoazo system: paratonere 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32, 112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267, 268,269。

Bisazo system: pigment red 3 7,38,41.

Monoazo color lake is: pigment red 4 8:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2, 53:1,53:2,57:1,58:4,63:1,63:2,64:1,68。

Benzimidazolone system: paratonere 171, paratonere 175, paratonere 176, paratonere 185, pigment Red 208.

System: solvent of red 135, solvent red 179, pigment red 123, pigment red 149, paratonere 166, Paratonere 178, pigment red179, paratonere 190, paratonere 194, paratonere 224.

Diketopyrrolopyrrolecocrystals system: paratonere 254, paratonere 255, paratonere 264, paratonere 270, Paratonere 272.

Condensation azo system: paratonere 220, paratonere 144, paratonere 166, pigment red 21 4, paratonere 220, paratonere 221, paratonere 242.

Anthraquinone system: paratonere 168, paratonere 177, pigment red 21 6, solvent red 149, solvent red 150, Solvent red 52, solvent red 207.

Quinacridone: pigment red 122, paratonere 202, paratonere 206, Pigment Red 207, paratonere 209。

Blue colorant:

As blue colorant, having phthalocyanine system, anthraquinone system, pigment system is classified as pigment (Pigment) Compound, specifically, following material can be listed: pigment blue 15, pigment blue 15: 1, alizarol saphirol 15:2, pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6, pigment blue 16, pigment blue 60.

As dyestuff system, it is possible to use solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, molten Agent indigo plant 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 19 22, solvent blue 19 36, solvent blue 67, solvent blue 70 etc..In addition to the foregoing, it is also possible to use metal replacement or unsubstituted phthalocyanine compounds Thing.

Green colourant:

As green colourant, there are phthalocyanine system, anthraquinone system equally, are, specifically, it is possible to use Pigment Green 7, pigment green 36, solvent green 3, solvent are green 5, solvent is green 20, solvent green 28 etc..Except upper Beyond stating, it is also possible to use metal replacement or unsubstituted phthalocyanine compound.

Yellow colorants:

As yellow colorants, have monoazo system, bisazo system, condensation azo system, benzimidazolone system, Isoindolinone system, anthraquinone system etc., specifically, can list following material.

Anthraquinone system: solvent yellow 16 3, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, Pigment yellow 199, pigment yellow 202.

Isoindolinone system: pigment yellow 110, pigment yellow 109, pigment yellow 13 9, pigment yellow 17 9, pigment Yellow 185.

Condensation azo system: pigment yellow 93, pigment yellow 94, pigment yellow 95, pigment Yellow 12 8, pigment yellow 155, Pigment yellow 166, pigment yellow 180.

Benzimidazolone system: pigment Yellow 12 0, pigment yellow 151, pigment yellow 154, pigment yellow 156, pigment Huang 175, pigment yellow 181.

Monoazo system: pigment yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97, 100,104,105,111,116,167,168,169,182,183。

Bisazo system: pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170, 172,174,176,188,198。

It addition, in order to adjust tone, purple, orange, brown, black etc. coloring agent can be added.

If particular instantiation, have pigment violet 19,23,29,32,36,38,42, solvent violet 13,36, C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. Pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. Pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. Pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73, C.I. Pigment brown 23, C.I. pigment brown 25, C.I. pigment black 1, C.I. pigment black 7 etc..

Can suitably be compounded aforesaid coloring agent, relative to 100 mass parts containing carboxyl oligomer or heat cure Property composition, below preferably 10 mass parts.More preferably 0.1～5 mass parts.

In the Photocurable resin composition of the present invention, can be compounded in molecule and there is multiple olefinic insatiable hunger Compound with group.The molecule that the Photocurable resin composition of the present invention is used has multiple alkene The compound belonging to unsaturated group is to be irradiated and photocuring by active energy ray, makes that the present invention's is photosensitive Property compound, aforementioned containing carboxyl photonasty oligomer insoluble in aqueous alkali or contribute to making photonasty Compound, the aforementioned photonasty oligomer containing the carboxyl material insoluble in aqueous alkali.As such compound, Usual known polyester (methyl) acrylate, polyethers (methyl) acrylate, carbamic acid can be used Ester (methyl) acrylate, carbonic ester (methyl) acrylate, epoxy (methyl) acrylate, carbamic acid Ester (methyl) acrylate etc., specifically, can list acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl The acrylic acid hydroxy alkyl ester classes such as ester；Ethylene glycol, methoxyl group TEG, Polyethylene Glycol, propylene glycol etc. two The diacrylate esters of alcohol；N, N-DMAA, N hydroxymethyl acrylamide, N, N-diformazan ammonia The acrylic amides such as base propylacrylamide；N, N-dimethylamino ethyl acrylate, N, N-dimethylamino The amino alkyl acrylates classes such as propyl acrylate；Hexanediol, trimethylolpropane, tetramethylolmethane, The polyhydric alcohol such as dipentaerythritol, three-hydroxyethyl isocyanuric acid ester or their ethylene oxide adduct, The multicomponent methacrylate classes such as propylene oxide adduct or 6-caprolactone addition product；Phenoxy group acrylate, Bisphenol a diacrylate and the ethylene oxide adduct of these phenol or propylene oxide adduct etc. are many Unit's esters of acrylic acid；Glycerin diglycidyl ether, T 55, trimethylolpropane tris contract The multicomponent methacrylate class of the glycidyl ethers such as water glycerin ether, triglycidyl group isocyanuric acid ester；And By polyhydric alcohol such as polyether polyol, PCDL, C-terminal polybutadiene, PEPAs Directly acroleic acid esterification or carry out urethane acrylate via diisocyanate and obtain third Olefin(e) acid esters and melamine acrylate and/or each methacrylate corresponding with aforesaid propylene acid esters Class etc..

Further, send as an envoy to polyfunctional epoxy resin and the propylene such as cresol novolak type epoxy resin can be enumerated Acid reaction and obtain Epocryl, make this Epocryl further hydroxyl with By hydroxy acrylate and the isophorone diisocyanate etc. such as pentaerythritol triacrylate two Carbimide. The epoxy amino formic acid esters acrylate chemical combination that half carbamate compounds that ester is formed reacts and obtains Thing etc..It is solid that such epoxy acrylate system resin improves light with can not reducing the dry to touch of film The property changed.

Such compound with multiple ethylenically unsaturated group can be used alone a kind or is applied in combination Two or more.From the viewpoint of photoreactivity and resolution, particularly preferred 1 molecule has 4 to 6 The compound of ethylenically unsaturated group, further, uses and has 2 ethylenically unsaturated groups in 1 molecule During compound, the linear expansion coefficient of solidfied material reduces, the generation of crackle when can reduce thermal cycling test, The most preferred.

Relative to containing carboxyl oligomer 100 mass parts, such molecule has multiple olefinic unsaturated group The compounding amount of the compound of group is preferably 5～100 mass parts.When compounding amount is less than 5 mass parts, photocuring Property reduce, it is difficult to the development of alkali after being irradiated by active energy beam forms pattern.On the other hand, super When crossing 100 mass parts, reducing the dissolubility of dilute alkaline aqueous solution, film becomes fragile.More preferably 1～70 matter Amount part.

Further, above-mentioned containing carboxyl oligomer, preparation compositions in order to synthesize, or in order to adjust viscosity To be applied in substrate, carrier film, the Photocurable resin composition of the present invention can use organic molten Agent.Such organic solvent can be used alone or uses as mixture of more than two kinds.

In the Photocurable resin composition of the present invention, for anti-oxidation, (1) can be added and make generation Free radical lost efficacy radical scavenger or/and the peroxide of generation is resolved into harmless thing by (2) The antioxidants such as matter, the peroxide decomposer not producing new free radical.

Further, in the Photocurable resin composition of the present invention, in addition to antioxidant, it is also possible to Use UV absorbent.

As such UV absorbent, can enumerate benzophenone derivates, benzoate derivatives, Benzotriazole derivatives, pyrrolotriazine derivatives, benzothiazole derivant, cinnamate (cinnamate) are derivative Thing, o-aminobenzoa (anthraxnilate) derivant, dibenzoylmethane derivatives etc..

As required, the Photocurable resin composition of the present invention can be compounded further known thermal resistance gather The known thickening agent such as agent, fine particle silica, organobentonite, montmorillonite, silicon system, fluorine system, height Defoamer and/or the levelling agents such as molecule system, the silane coupler such as imidazoles system, thiazole system, triazole system, antioxygen Agent, the most known additive kind such as antirust agent.

In the Photocurable resin composition of the present invention, in order to improve interlayer adaptation or can be formed The adaptation of resin insulating barrier and base material and use closely sealed accelerator.As such closely sealed accelerator Example, for instance that benzimidazole, benzothiazole, benzothiazole, 3-morpholinomethyl-1-phenyl-three Azoles-2-thioketone, 5-amino-3-morpholinomethyl-thiazole-2-thioketone, triazole, tetrazolium, benzotriazole, carboxylic Base benzotriazole, containing amino benzotriazole, silane coupler etc..

The Photocurable resin composition of the present invention so constituted is after being prepared as composition requirement, such as, Be adjusted to be suitable to the viscosity of coating process with organic solvent, and by dip coating, flow coat method, rolling method, The methods such as scraper rubbing method, silk screen print method, curtain coating are applied on base material.

Further, at a temperature of about 60～100 DEG C, organic solvent volatile dry contained in compositions is made (temporarily Time be dried), form not viscous film (resin insulating barrier).Now, volatile dry can use hot blast to follow (use has the air heating side utilizing steam for ring type drying oven, IR stove, hot plate, convective oven etc. The device of the thermal source of formula, makes method that the hot air convection in drying machine contacts and blows supporter by nozzle Mode) carry out.

Furthermore it is also possible to by being formed dry film by Photocurable resin composition and being fitted to base material On, form resin insulating barrier.

Dry film has a structure of the following material of stacking in the following order: such as poly terephthalic acid second The resin insulating barriers such as the carrier film of diol ester etc., solder mask, the strippable coverlay used as required.

Resin insulating barrier is to be applied on carrier film or coverlay by Photocurable resin composition and be dried And the layer obtained.Such resin insulating barrier is that the Photocurable resin composition of the present invention is passed through scraper Coating machine, lip coating machine (lip coater), comma coater (comma coater), film coater Formed Deng being uniformly applied in carrier film with the thickness of 10～150 μm and be dried.Further, also may be used To form dry film as desired by laminated cover film.Now, it is also possible to light-cured resin is combined Thing is applied on coverlay and dried, stacking carrier film.

As thermoplastic films such as carrier film, the such as mylars that thickness can be used to be 2～150 μm.

As coverlay, it is possible to use polyethylene film, polypropylene film etc., it is bonding with solder mask Preferable little with the bonding force of carrier film of force rate solder mask.

Use such dry film, after being peeled off in the case of using coverlay, make resin insulating barrier Overlapping with base material, use laminating machine etc. to fit, base material is formed resin insulating barrier.It addition, carry Body film is peeled off before exposure described later or after exposure.

Now, as forming film or the base material of laminating dry film, can list and employ paper-phenolic aldehyde Resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimides, glass cloth/non-woven fabrics-ring Epoxy resins, glass cloth/paper-epoxy resin, synthetic fibers-epoxy resin, fluorine polyethylene PPO cyanate Deng high-frequency circuit copper-clad laminated board etc. material all grades (FR-4 etc.) copper-clad laminated board, And Kapton, PET film, glass substrate, ceramic substrate, wafer board etc..

Further, contact (or cordless) is used to make active energy beam by being formed with pattern Photomask optionally expose or utilize the direct exposure machine of laser directly to carry out pattern exposure.It is coated with The exposure portion (part irradiated by active energy beam) of film is cured.

As the exposure machine used by active energy beam irradiation, it is possible to use directly drawing apparatus is (the most logical Cross the cad data from computer and utilize the laser direct imaging device of laser direct depiction picture), take It is loaded with the exposure machine of metal halide lamp, is equipped with the exposure machine of (surpassing) high voltage mercury lamp, is equipped with hydrargyrum The exposure machine of short-arc lamp or employ the direct drawing apparatus of the Burdick lamps such as (surpassing) high voltage mercury lamp.

As active energy beam, maximum wavelength laser 350～410nm in the range of is preferably used. By making maximum wavelength within the range, can effectively be produced free radical by Photoepolymerizationinitiater initiater.If making With the laser of this scope, then can use gas laser, Solid State Laser any one.Additionally, its exposure Measure according to thickness etc. different, typically 5～500mJ/cm², preferably 10～300mJ/cm²'s In the range of.

As direct drawing apparatus, Orbotech Japan Co., Ltd. such as can be used to manufacture, The device of PENTAX CORPORATION manufacture etc., as long as vibration maximum wavelength is 350～410nm The device of laser, then can use arbitrary device.

Further, by being so exposed, exposure portion (part irradiated by active energy beam) is made Solidification, utilizes dilute alkali aqueous solution (such as, 0.3～3wt% aqueous sodium carbonate) to enter unexposed portion Row development, forms solidfied material (pattern).

Now, as developing method, it is possible to use infusion process, elution method, nebulization, spread coating etc.. As developer solution, it is possible to use potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, silicon The alkaline aqueous solution of acid sodium, ammonia, amine etc..

Further, when adding heat curable component, the such as temperature by being heated to about 140～180 DEG C makes it Heat cure, makes have multiple cyclic ether group and/or ring-type sulfur in the carboxyl containing carboxyl oligomer and such as molecule The heat curable component of ether reacts, it is possible to formed thermostability, chemical proofing, resistance to hygroscopicity, The solidfied material (pattern) of all excellents such as adaptation, electrical characteristics.

So, by light curing resin composition containing containing carboxyl oligomer, molecular weight ratio is aforementioned contains High polymer binder that carboxyl oligomer is big, Photoepolymerizationinitiater initiater, photopolymerization monomer, filler, it is solid Compound can obtain being applied to the reliabilities such as thermostability required during electronic unit etc., cold-hot cyclicity Without damaging resistance to migration characteristic.Further, by such solidfied material is used in printed circuit board (PCB) etc., High reliability can be obtained.

Embodiment

Below, it is shown that the present invention is specifically illustrated by embodiment and comparative example, but the present invention is not subject to down State the restriction of embodiment.Additionally, following " part " and " % ", without particularly limiting, all Refer to quality criteria.

Synthesis example 1

Possessing thermometer, nitrogen gatherer holds concurrently the autoclave of alkylene oxide gatherer and agitating device In, add 119.4 parts of phenolic varnish type cresol resins (trade name " Shonol CRG951 ", Showa high score Son (strain) manufactures, OH equivalent: 119.4), 1.19 parts of potassium hydroxide and 119.4 parts of toluene, while stirring To carrying out nitrogen displacement, heat temperature raising in system.Then, slowly 63.8 parts of expoxy propane of dropping, 125～ 132 DEG C, 0～4.8kg/cm²Lower reaction 16 hours.It is then cooled to room temperature, adds in this reaction solution 1.56 part of 89% phosphoric acid mixing neutralize potassium hydroxide, thus obtain nonvolatile component 62.1%, hydroxyl Value is the propylene oxide reaction solution of the phenolic varnish type cresol resin of 182.2g/eq..It is every 1 equivalent phenol The property average addition of hydroxyl has the addition product of 1.08 mol of alkylene oxide.

By the alkylene oxide reaction solution of 293.0 parts of obtained phenolic varnish type cresol resins, 43.2 parts of propylene Acid, 11.53 parts of Loprazolams, 0.18 part of methylnaphthohydroquinone and 252.9 parts of toluene join and possess blender, temperature Degree meter and air are blown in the reactor of pipe, are blown into air with the speed of 10ml/ minute, while stirring 110 React 12 hours at DEG C.About the water generated by reaction, the water of 12.6 parts is as the azeotropic with toluene Mixture distillates.It is then cooled to room temperature, with anti-with gained in 35.35 part of 15% sodium hydrate aqueous solution Answer solution, then wash.Thereafter, in vaporizer by toluene limit by 118.1 parts of diethylene glycol list second The distillation of ether acetic acid ester interchange limit is removed, thus obtains phenolic varnish type acrylic ester resin solution.Then, 332.5 parts of gained phenolic varnish type acrylic ester resin solutions and 1.22 parts of triphenylphosphines are joined and possess Agitator, thermometer and air are blown in the reactor of pipe, are blown into air with the speed of 10ml/ minute, It is slowly added to 60.8 parts of tetrabydrophthalic anhydrides while stirring, reacts 6 hours at 95～101 DEG C, cooling Rear taking-up.Thus, obtain nonvolatile component 65%, the acid number of solid matter is containing of 87.7mgKOH/g The solution (hereinafter referred to as A-1) of carboxyl photonasty oligomer (Mw:2650).

Synthesis example 2

By 330 parts of cresol novolak type epoxy resins (Epiclon N-695, Dainippon Ink Chemicals manufacture, Epoxide equivalent 220) add in the flask possessing gas introduction tube, agitating device, cooling tube and thermometer, Add 340 parts of carbitol acetate (Carbitol acetate), heating for dissolving, add 0.46 part of hydroquinone and 1.38 Part triphenylphosphine.This mixture is heated to 95～105 DEG C, is slowly dropped into 108 parts of acrylic acid so that it is be anti- Answer 16 hours.This product is cooled to 80～90 DEG C, adds 68 parts of tetrabydrophthalic anhydrides, instead Answer 8 hours so that it is cooling.Thus, the acid number obtaining solid matter is 50mgKOH/g, non-volatile one-tenth Divide the solution (hereinafter referred to as A-4) of the photonasty oligomer containing carboxyl (Mw:9500) of 60%.

Embodiment 1～16 and comparative example 1～3

Use the resin solution of above-mentioned synthesis example, with shown in table 1 together with the various compositions shown in table 1 below Ratio (mass parts) compounding, use blender premixing, then carry out mixing with 3 roll-type roller mills, Prepare solder resist photosensitive polymer combination.

[table 1]

The meaning of the reference marks in above-mentioned table 1 is as follows.

* 1:ZFR-1124 (nonvolatile component 65.0%, solid constituent acid number 100mgKOH/g, Mw:11500, Japan's chemical medicine (strain) manufacture)

* 2:ZCR-1601H (nonvolatile component 65.0%, solid constituent acid number 100mgKOH/g, Mw:1730, Japan's chemical medicine (strain) manufacture)

* 3:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1,1-(O-acetyl oxime) ethyl ketone (BASF JAPAN company manufacture)

* 4:Lucirin TPO (BASF AG's manufacture)

* 5:Nippon Talc Co., Ltd. manufacture SG-2000 (refractive index: 1.57)

* 6: chemical industry (strain) manufactures B-33 (refractive index: 1.64)

* 7: Showa electrician (strain) manufactures Higilite H-42M (refractive index: 1.65)

* the Kaolin of 8:Sillitin(tabular and the natural binder of spherical silicon dioxide, refractive index: 1.57)

* 9:Admatechs Company Limited SO-E2 (refractive index: 1.45)

* 10: consonance chemical industry (strain) DHT-4A processed (refractive index: 1.50)

* 11 Nippon Steel Chemical Co., Ltd manufacture YP-50(phenoxy resin, Mw: about 70000)

* 12 Nippon Steel Chemical Co., Ltd manufacture the carbitol acetate of YP-50 and dissolve product (solid constituent 30%)

* 13ARKEMA LTD. manufacture MAM-M51(ternary block polymer: polymethylacrylic acid Methyl ester-butyl polyacrylate-polymethyl methacrylate, Mw: about 56000)

* 14ARKEMA LTD. manufacture MAM-M52(ternary block polymer: polymethylacrylic acid Methyl ester-butyl polyacrylate-polymethyl methacrylate, Mw: about 96000)

* 15ARKEMA LTD. manufacture SBM-E41(ternary block polymer: polystyrene-poly fourth two Alkene-polymethyl methacrylate, Mw: about 42000)

* 16Eastman Chemical company manufactures CAP-482(cellulose acetate propyl ester, Mw: about 75000)

* 17 Japan's weaving (strain) manufacture Byron670(amorphous polyester resin, Mn: about 30000)

* 18: di-toluene phenol-type epoxy resin (Mitsubishi Chemical's (strain) manufacture)

* 19: bisphenol-type epoxy resin (Nippon Steel's chemistry (strain) manufactures)

* 20:C.I. pigment blue 15: 3

* 21:C.I. pigment yellow 147

* 22: dipentaerythritol acrylate (Japan's chemical medicine (strain) manufactures)

Attribute testing:

Pass through silk screen printing whole topcoating cloth previous embodiment on figuratum copper clad laminate being formed and compare Each compositions of example, naturally cools to room temperature after being dried 30 minutes at 80 DEG C.Use is equipped with high-pressure mercury Soldering-resistant pattern is exposed by the exposure device of lamp on the substrate with optimum exposure, with 30 DEG C 1wt% aqueous sodium carbonate carries out development in 90 seconds under conditions of spraying 0.2MPa, obtains corrosion-resisting pattern. This substrate is transmitted in stove in cumulative exposure amount 1000mJ/cm at UV²Under conditions of carry out ultraviolet photograph Penetrate, then heat at 160 DEG C and solidify for 60 minutes.Printed base plate (evaluation substrate) to gained It is carried out as follows evaluating characteristics.

＜ optimum exposure ＞

Circuit pattern substrate polishing roll that copper thickness is 35 μm is ground, then washing, dried, logical Cross silk screen print method whole topcoating cloth previous embodiment and each compositions of comparative example, by the hot air circulation of 80 DEG C Formula kiln dried 30 minutes.Afterwards, use is equipped with the exposure device of metal halide lamp (HMW-680-GW20) it is exposed by the 41 of stauffer grades of stage actinometers, will develop (30 DEG C, 0.2MPa, 1wt%Na₂CO₃Aqueous solution) 60 seconds time residual the pattern of stage actinometer when being 7 sections Light exposure as optimum exposure.

＜ coating ＞

Carry out whole topcoating cloth by silk screen printing on figuratum copper clad laminate being formed and confirm to print shape State.Determinating reference is as follows.

◎: do not have uneven, to keep ink against corrosion thickness on pattern.

Zero: produce a part of uneven on pattern, keep the thickness of ink against corrosion.

×: the ink on pattern is thinning.

＜ chemically-resistant gold-plated property ＞

Use electroless nickel bath and the chemical gilding bath of commercially available product, in nickel 0.5 μm, the condition of golden 0.03 μm Under carry out plating, peeled off by band evaluate resist layer with or without peel off, plating solution with or without infiltration, then, Peeled off by band and evaluate resist layer with or without stripping.Determinating reference is as follows.

◎: can not see infiltration, can not see stripping.

Zero: confirm a little infiltration after plating, but band is not peeled off after peeling off.

△: only see a little infiltration after plating, band can also see that stripping after peeling off.

×: there is stripping after plating.

＜ resistance to PCT ＞

Put into 121 DEG C, 2 air pressure, humidity 100% high pressure-temperature height wet sump in 168 hours, according to Under metewand evaluate cured coating film state change.

◎: significantly expansion, variable color do not occur.

Zero: have small expansion, there is no variable color.

×: occur significantly expanding, having variable color.

The resistance to anti-thread breakage ＞ of ＜

Will at-55 DEG C 30 minutes, at 125 DEG C 30 minutes as 1 circulation, apply thermal history, through 1000 After circulation, observe under an optical microscope.Determinating reference is as follows.

◎: do not have crackle to produce.

Zero: have crackle to produce.

×: crackle produces substantially.

＜ resolution ＞

The substrate be formed with plating coating copper utilizes each of silk screen print method coating Examples and comparative example Light solidifying/heat solidifying resin composition, is dried 30 minutes in the heated air circulation type drying oven of 80 DEG C. After drying, the exposure device being equipped with high voltage mercury lamp (short-arc lamp) is used to be exposed.Exposing patterns uses Describe the glass dry plate having the circle of opening 50/60/70/80/90/100 μm.It is photoresist by light exposure The mode of the optimum exposure of compositions irradiates active energy beam.After exposure, with the 1wt% carbon of 30 DEG C Acid sodium aqueous solution carries out developing 90 seconds under conditions of spraying 0.2MPa, obtains corrosion-resisting pattern.By this base Plate transmits in stove in cumulative exposure amount 1000mJ/cm at UV²Under conditions of carry out ultraviolet irradiation, then Heat at 160 DEG C and solidify for 60 minutes.

The optical microscope adjusted to 200 times is used to obtain gained solder resist photosensitive polymer combination The minimal openings of cured coating film.Determinating reference is as follows.

◎: less than 60 μm.

More than zero: 60 μm～less than 80 μm.

More than △: 80 μm and less than 100 μm.

×: more than 100 μm.

＜ linear expansion coefficient ＞

Cured coating film to 3mm × 10mm size, lateral dominance Seiko Instruments Inc. manufactures TMA6100 applies the load limit of 10g and carries out the temperature range of 0 DEG C-260 DEG C with certain programming rate Tension test.Linear expansion coefficient is calculated by the elongation of the cured coating film relative to temperature.

The result of above-mentioned each test is collected and is shown in table 2.

[table 2]

As shown in Table 2 above, use in each embodiment of Photocurable resin composition of the present invention, be coated with The gold-plated property of cloth, chemically-resistant, resistance to PCT, resistance to anti-thread breakage equal excellence.On the other hand, height it is not compounded In the case of the comparative example 1 of molecular binder, it will be apparent that become swollen mecystasis, be difficult to be coated with.Enter one Step, resolution is also deteriorated.On the other hand, compounded with high polymer binder but be not compounded the comparison of filler In the case of example 2, coating, resolution are no problem, but could not reduce linear expansion coefficient, resistance to cracking Stricture of vagina is deteriorated.Further, since do not contain filler, the moisture such as plating solution becomes to easily infiltrate into, chemically-resistant plating Gold and resistance to PCT are deteriorated.It addition, in the case of the few comparative example 3 of the compounding amount of filler also Linear expansion coefficient, resistance to anti-thread breakage existing problems could not be reduced fully.

Industrial applicability

The Photocurable resin composition of the application of the invention, even if compounding filler is as solder resist in a large number Process also good, the generation of solder mask crackle, the stripping that produce during cold cycling can be suppressed, therefore The layer insulation material of the solder resist such as printed circuit board (PCB), flexible PCB, multilayer circuit board can be suitable for Material etc., the especially formation of semiconductor-sealing-purpose solder resist.

Claims

1. the Photocurable resin composition that can be developed by aqueous slkali, it is characterised in that this group Compound comprises containing the big high polymer binder of the oligomer Han carboxyl described in carboxyl oligomer, molecular weight ratio, light Polymerization initiator, photopolymerization monomer and filler, described high polymer binder is ethyl cellulose, vinegar Acid cellulose, acetyl propyl cellulose, acetyl tributyl cellulose, cellulose acetate propyl ester or by use The block copolymer that the monomer with vinyl of more than two kinds carries out being polymerized and obtains, described macromolecule glues The weight average molecular weight of knot agent is 30000～1500000, and the content of described filler is the non-volatile of compositions 30～60 mass % of composition total amount.

Photocurable resin composition the most according to claim 1, it is characterised in that described high score Sub-binding agent is thermoplastic resin.

Photocurable resin composition the most according to claim 2, it is characterised in that described thermoplastic The solid constituent that property resin is dissolved under same solvent state is 10～50wt%.

Photocurable resin composition the most according to claim 1, it is characterised in that described filler Comprise Ba or comprise Mg and/or Al.

5. a dry film, it is to be combined by the light-cured resin according to any one of Claims 1 to 4 Thing is the most coated and dried and obtains.

Dry film the most according to claim 5, it is characterised in that dry film is by multilayer optical curable resin The drying layer of compositions is constituted, and at least one of which is by the photo-curable tree described in any one of Claims 1 to 4 Oil/fat composition is formed.

7. a solidfied material, it is characterised in that it is solid by the light according to any one of Claims 1 to 4 The property changed resin combination is coated on base material, carries out photocuring by the irradiation of active energy beam and obtains Arrive.

8. a printed circuit board (PCB), it is characterised in that having the pattern of solidfied material, described solidfied material is such as Under obtain: the Photocurable resin composition according to any one of Claims 1 to 4 is coated with on base material And be dried, carry out photocuring by the irradiation of active energy beam and obtain.

9. a solidfied material, it is characterised in that its by the dry film lamination described in claim 5 or 6 at base On material, carry out photocuring by the irradiation of active energy beam and obtain.

10. a printed circuit board (PCB), it is characterised in that having the pattern of solidfied material, described solidfied material is such as Under obtain: by the dry film lamination described in claim 5 or 6 on base material, by the photograph of active energy beam Inject row photocuring and obtain.